Pi-allyl nickel compounds and their preparation



United States Patent Ofifice St 20,975 US. Cl. 260-439 11 Claims Int. Cl. C08f 1/32; C07f 15/04; C07f 15/00 ABSTRACT OF THE DISCLOSURE Production of 11' allyl nickel compounds by the reaction of a nickel olefinic hydrocarbon compound with allyl halides and products produced thereof. The compounds have utility as oligomerization and polymerization catalysts.

This invention relates to new and useful improvements in 1rallyl-metal compounds. I have discovered that 1rallyl compounds of the transition metals of side Groups III to VIII, and especially those of the IVth to VIIIth groups of the Periodic System, are as such, or in combination with other materials, for example Lewis acids and/ or electron donors, such as Lewis bases and the like, excellent polymerization (including oligomerization) catalysts and especially for the production from monoand diolefins of open chain oligomers and of higher molecular weight polymers. The obtaining of such 1r-allyl compounds for which the elfective grouping is in which Me is a transition metal of the IIId to VIIIth side groups of the Periodic System and preferably of the IVth to VIIIth such group, and n is an integer of 14, has been set forth in my co-pending application, Ser. No. 272,881 and their use as polymerization catalysts is set forth in my co-pending application, Ser. No. 387,826, filed Aug. 6, 1964, corresponding to my corresponding German application, Ser. No. 20,976, filed in Germany about Aug. 10, 1963. Said last mentioned co-pending =ap plication further sets forth as polymerization catalysts such 1r-allyl compounds for which the effective grouping is I l I XmMe l Me having the same meaning as above, X designating an anionic radical, and m and n each designating an integer of 13 with m+n being 2-4.

One object of the invention comprises the production of certain specific compounds of the above type, i.e. 7rallyl-Ni-halides of the general Formula I in which X signifies a halogen and R to R which may be similar or different, signify hydrogen, alkyl, cycloalkyl, aralkyl or aryl, wherein the radicals R or R or R and R or R may also be bound into an olefinic unsaturated ring system, with at least 3 to 4 and preferably 5-12 ring members. As shown by the formula these compounds exist as dimers and it is characteristic that the nickel is bound therein to a rr-allyl-system or 1r-allyl-systems, and in the simplest case to the 1r-3llYl-gIOLlP as such or its hydrocarbon, i.e. alkyl, aryl, or aralkyl and 3,422,128 Patented Jan. 14, 1969 their cyclic derivatives. A 1r-allyl-system is defined as a grouping of 3 C'atoms, which is bound as a substantially planar system to a central atom in substantially the same manner by way of all 3 C-atoms.

In the simplest case of the bis-1r-allyl-nickel with an empirical Formula II (C H Ni this type of bond is represented as follows:

The roentgenographic structural analysis of the corresponding methyl derivative, the bis-1r-methallyl nickel, has shown that a sandwich type compound is involved in which the two methallyl groups are bound to the nickel atom as planar systems in such manner that the CH groups go into the anti-position:

eff

In the compounds of type I, producible in accordance with the invention, one each such planar 1r-allyl-system is bound to a nickel atom.

Some compounds of the type 1r-allyl-Ni-X are already known. Thus E. O. Fischer and G. Biirger (Z. Naturforsch., 16b, 77 (1961), report 94, 240 9 (1961)) have for the first time described the preparation of the vr-allylnickelbromide from the extremely poisonous nickelcarbonyl and allylbromide. The yields were given as only 11% of theory.

I have found that 1r-allyl-nickelhalides of the general Formula I may be produced very easily through action of the corresponding allylhalides on olefinic, i.e., only olefinically unsaturated hydrocarbons containing complexes of the nickel. Herein compounds are obtained in which the 1r-allyl-system according to the following Formula II is contained:

,9 Rs s N1 X NiBr 2COD C O D =Oyclooctadiene (1,5)

The reaction in accordance with the invention may be carried out either in the presence of a solvent inert for the reaction partners, or, if the allylhalide is liquid, without solvent. Suitable solvents are aliphatic saturated or aromatie hydrocarbons, and aliphatic or aromatic halogenated hydrocarbons or similar materials, including chlorbenzol, tetrahydrofuran and anisol and the like. Advantageously, the reaction is carried out at temperatures of from 20 to +20 C.

The great advantage of the process in accordance with the invention lies therein that, easily accessible and above all, harmless starting materials are used, and that the desired products are produced directly in substantially pure form and in practically quantitative yield without purification being necessary.

All operations must be carried out under exclusion of air and humidity, i.e., under protective gas, such as for example argon or nitrogen, since the compounds producible in accordance with the invention are sensitive to air or humidity.

EXAMPLE 1 2.1 g. biscyclooctadiene-nickel-(O) are suspended in 100 cm. ether and mixed at 10" with a solution of 1 g. allylbromide in ether under stirring. The solution becomes colored deep red and the yellow crystals of the starting complex go into solution. The ether is distilled oil in vacuum, and the cyclooctadiene is removed at 10- torr and 20. Obtained are 1.2 g.=90% of the theory of vr-allylnickelbromide, which is somewhat volatile at 10- torr.

Calculated: Ni, 32.7%. Found: Ni, 32.1%.

EXAMPLE 2 To a suspension of 7.15 g. cyclooctatetraene-nickel-(O) in 100 cm. toluene is added drop by drop at 20 under stirring, a solution of 5.3 g. allylbromide in toluene. The solution becomes colored deep red and the crystals of the starting complex go slowly into solution. The red solution is filtered and freed at 10* torr from solvent and cyclooctatetraene. Obtained are g.63% of the theory 1r-allylnickelbromide.

Calculated: Ni, 32.7%. Found: Ni, 32.0%.

EXAMPLE 3 Into a mixture of 1.57 g. tris-bicycloheptene-nickel-(O) in 100 cm. toluene is added drop by drop at 30 a solution of 6.1 g. allylbromide in toluene under stirring. Obtained is a deep red solution, which is warmed to room temperature and then filtered. The solvent is distilled olf in vacuum, and the residue dried at torr. The product is recrystallized from ether, and obtained is a red powder of the composition C H NiBr-C H i.e. it is a 7r8.llylnickelbromide, to which is still complex-bound a bicycloheptene-molecule.

Calculated: Ni, 21.4%. Found: Ni, 21.0%.

EXAMPLE 4 A suspension of 4.9 g. bis-cyclooctadiene-nickel-(O) in 100 cm. toluene is converted at 20 with a solution of 2.7 g. cinnamylchloride in toluene under stirring. Subsequently the suspension is stirred for two hours at 5 to 10. Toluene and cyclooctadiene are distilled off in vacuum and the residue dried at 10* torr. The reaction product is dissolved in ether, filtered, and the clear solution cooled to Therein the 1r-cinnamylnickelchloride is separated in the form of red shining crystals of the composition C H ClNi.

Calculated: Ni, 27.8%. Found: Ni, 27.8%.

EXAMPLE 5 7.5 g. bis-cyclooctadiene-nickel-(O) are suspended in cm. ether and converted at 20 with a solution of 6.0 g. l-chloro-cyclooctene-(2). Obtained is a clear red solution which is evaporated in vacuum. The residue is dried at 10' torr and freed from cyclooctadiene. The reaction product is recrystallized from ether. Obtained are 4.2 g.=81% of the theory of vr-CYCIOOClZCIlYl-niCkClchloride.

Calculated: Ni, 28.9%. Found: Ni, 28.8%.

EXAMPLE 6 According to Example 5 biscyclooctadiene-nickel-(O) is converted with l-chlorocyclohexene-(Z). Obtained is a red solution which contains the 1r-cyclohexenyl-nickelchloride.

EXAMPLE 7 According to Example 5 bis-cyclooctadiene-nickel is converted with cyclododecatrienylchloride. Obtained is a red solution which contains a 1r-cyclododecatrienyl-nickelchloride.

EXAMPLE 8 8.4 g.=30.5 mmol. bis-cyclooctadiene-nickel-(O) are dissolved in 30 cc. of toluene and there is dropwise added at 40 C. 3.5 g.=24.1 mmol. of 3-chlor-cyclopentene. In the course of the addition, the yellow solution turns dark red. Traces of metallic nickel were separated and removed. The clear solution is concentrated to dryness after 36 hours at 10- torr. The red colored residue is extracted with pentane. There then remains undissolved the vr-cyolopentenyl-nickelchloride. The red product is filtered off and dried. There are then obtained 3.5 g.=71.5% Of theory of 1r-cyclopentenyl-nickelchloride.

Calculated: Ni, 36.4%. Found: Ni, 36.8%.

EXAMPLE 9 6.1 g.=22.2 mmol. bis-cyclooctadiene-nickel-(O) are dissolved in 50 cc. of toluene, whereupon there is added at 20 C. 4.1 g=24.5 mmol. of benzylallylchloride (1-phenyl-4-chl0r-butene-(2)) dissolved in 40 cc. of toluene. The yellow colored solution turns red. The toluene is removed at 10 torr and the orange-red colored residue is then extracted with pentane. The red colored product is then filtered off and dried in vacuo. There are obtained 4 g.=80% of theory of the benzyl-1r-allyl-nickelchloride.

Calculated: Ni, 26.04%. Found: Ni, 25.6%.

EXAMPLE 10 82.0 g.=0.3 mol. of bis-cyclooctadiene-nickel-(O) are suspended in 300 cc. of ether, whereupon there is added at 20 C. with vigorous stirring, a solution of 40 g.=0.33 mol. of allylbromide Within a period of 34 hours. After the reaction is completed, the mixture is cooled down to 80. There then precipitates the ar-allyl-nickelbromide which is filtered 01f.

Calculated: Ni, 32.6%. Found: Ni, 32.2%.

EXAMPLE 1 1 51.2 g.=0.186 mol. of bis-cyclooctadiene-nickel-(O) are suspended in 750 cc. of ether, whereupon there is added a solution of 33.3 g.=0.206 mol. allyliodide in 200 cc. ether with vigorous stirring within a period of 3 hours at 10 C. The mix is thereafter heated to 0 and stirring is continued until the crystals of the starting complex have completely dissolved. One now cools to 80 C. and filters off the separated 1r-fll1Y1-Ill6k6ll0dld6. The yield is 34.1 g.=80% of theory.

Calculated: Ni, 25.9%. Found: Ni, 25.5%.

EXAMPLE 12 23 g.=83.6 mmol. bis-cyclooctadiene-nickel-(0-) are suspended in 50 cc. of ether and are then admixed at 20 C. in the course of 15 hours with a solution of 19.8 g.=92.2 mmol. myrtenylbromide in 50 cc. ether with stirring. After about 36 hours the starting complex material has been converted. The solution is filtered at 20" C. and is thereafter cooled to 80 C. The red crystals separate. They are filtered off at a low temperature and are dried at torr. There is obtained 10.5 g.=46% of theory of pure 1r-pinenyl-nickelbromide.

EXAMPLE 13 6.9 g.=25 mmol. bis-cyclooctadiene-nickel-(O) in 8 cc. of toluene are admixed at 10 C. with a suspension of 10 g. of 1,2,3triphenyl-cyclopropenylbromide in 30 cc. of toluene. The mixture is stirred for a period of 24 hours. Thereafter all of the volatile components are distilled off at 10' torr and the residue is thereafter crystallized from toluene at +60 C. There are obtained 7 g.=69% of theory of 1,2,3-triphenyl-arcyclopropenyl-nickelbromide.

The properties, activity and reactivity of the 1r-allyl Ni compounds herein described are solely due to the 1r-allyl linkage and the particular stereo positioning of atoms thereby defined. Thus their effective grouping which is controlling for said properties, activity and reactivity is fittings] (X being halogen) regardless of any particular substituent. Similarly the reactivity in accordance with the invention of the olefinically unsaturated cyclohydrocarbon Ni compounds is based upon the therein inherent lability of the hydrocarbon linkage regardless of any substituents, while the reactivity of the allylhalide is based upon the particular configuration of the grouping and the relative lability imparted to the halogen thereby, substantially unaffected by any substituents including those incorporating the alkyl chain itself into a ring system. This is well illustrated by the fact that small and long chain aliphatic substituents, cyclic substituents including those of the bulky pinenyl and various aromatic substituents, all as shown by the at-times highly substituted or cyclo-allyl halides used, do not affect their basic reactivity in accordance with the invention.

Polymerization by the use of the compounds in accordance with the invention may be effected by, for instance, contacting the same with a monoor diolefin or contacting such compound in combination with a Lewis acid and/or a Lewis base (electron donor) with such monoor diolefin.

I claim:

1. Method for the production of a vr-nickel-allyl compound having an anionic radical linked thereto, which comprises reacting a nickel cycloolefinic hydrocarbon compound with an allyl halide.

2. Method in accordance with claim 1 in which said halide is one selected from the group consisting of chloride, bromide and iodide.

3. Method in accordance with claim 2 in which said reacting is carried out in liquid phase.

. 1r-cinnamyl-nickelchloride.

. 7r-cyclooctenyl-nickelchloride.

. ar-cyclododecatrienyl-nickelchloride.

. ar-cyclopentenyl-nickelchloride.

. benzyl-1r-allylnickelchloride.

11. 1,2,3-triphenyl-1r-cyclopropenyl-nickelbromide.

References Cited UNITED STATES PATENTS 3,159,658 12/1964 Fischer et al 260-429 OTHER REFERENCES Jones et al.: Tetrahedron Letters, No. 2 (1961), pp.

A. P. DEMERS, Assistant Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,422,128 January 14, 1969 Giinther Wilke It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 43, "alkyl" should read allyl Signed and sealed this 17th day of March 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr. 9 WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents 

